Wax phenol-phosphorus pentoxide reaction products and petroleum oil fractions containing the same



points. 'taining. these products-which. are strongly resistant to United States Patent Office 2,698,835 Patented Jan. 4, 1955 WAX PHENOL-PHOSPHORUS PENTOXIDE REAC- TION- PRODUCTS AND PETROLEUM OIL FRAC- TIONS'CONTAINDIG THE SAME Ferdinand P. Otto, Wo01lbury", N. J., assignor to Socony- Vacuum Oil Company, Incorporated, a corporation of New York No Drawing, Application-June, 1950, Serial No. 171,226

3'Claims. (Cl. 25249.8)'

This invention relates to anovelclass of chemical compounds prepared'by the reaction of wax-substituted hydroxy aromatic compounds-with phosphorus pentoxide. Moreparticularly, theinvention is concerned with the use of 'Ithese/cotnpound's as. additives forv petroleum oil fractions to improve the properties thereof.

The use of chemical. additives in petroleum oil fractions, such as lubricating oils, fuel oils, gasolines, etc., to improve thelproperties thereof iswellnknown. Thus, in lubricating oil, additives have been used for the purposeofimproving the ability of the oil to resist oxidation in use, for improving the detergent action of the oil, for lowering the pour point, for. increasing the viscosity indexgnfor raising the load-carrying capacity of the oil, etc.- Additives have also been used in'diesel fuels for various purposes, suchasto improve-ignition quality or to lower the startingtemperatures thereof. They have also been used in gasolines for numerous purposes, such asto' improve octane ratings and -to' prevent gum formation and to inhibit theforma-tion of ruston" metallic surfaces in contact with the gasoline in pipelines and in storage.

We have. now'found that the productsherein contemplated, i; e; the products obtained by reacting a wax- .alkylated hydroxy aromatic compound, such as wax phenol, with phosphoruszpentoxide, are capable; of providing certain beneficial properties, when usedas additives, in petroleumoit fractions,.particularly in mineral lubricating oils and gasolines.

In particular,we have found that these compounds are capable of greatly increasing the load-carrying capacities, as well as markedly lowering the pour points, of petroleum lubricating oils. Also, they are very effective as rustinhibitors in gasolines. Accordingly, it is the object of this invention. to provide petroleum oil fractions of improved characteristics, said fractions containing minor proportions of the products herein contemplated.

It is a further object to provid'epetroleum lubricating oils containing these products: which oils have. relatively high load-carrying capacities and" relatively low pour It is also an obiect to provide gasolines conthehformation ofrust on metal" surfaces incontact'there- Wlt It is realized that products of a somewhat similar character to those contemplated'herein have been usedheretofore as additives in mineral lubricating oils. Specifically, products prepared by the reaction of phosphorus pentoxide with alkylatedhydroxy aromatic compounds, in which the'alkyl groups are of relatively short chain length'as' compared to thewax group substituents of the wax alkylated hydroxy aromatic compounds. us'edherein. As far as is known, however, products of the present type, i. e. wherein the alkyl substituent groups are of wax origin, have not been.used in such applications heretofore and, in fact; have not been prepared heretofore.

In accordance with this invention, it has been found that the:wax-allcylatedphenolephosphorus: pentoxide products are unexpectedly superior to the products obtained by the-reaction of the lower' alkyl phenols with phosphorus pentoxide asaddition agents for: petroleum oil fractions, as'w-ill be demonstrated hereinafter. In particular, we have found thatthe wax-alkylated phenolpliosphorus pentoxide'products' are highly'superior to the non-wax alkylated.phenolwphosphorus-pentoxide products as extreme pressure agents for mineral lubricating oils and as rust inhibitors in gasoline.

In preparing theproducts herein contemplated, the wax-alkylated hydroxy aromatic compound and the phosphorus pentoxide are heated together at a temperature of from about 50 C. to about C. for a period of time sufiicient to insure substantially complete reaction, usually from about 5 to about 15 hours. Aninert solvent such as toluene, Xylene or the like may be used to facilitate. the reaction. A mineral lubricating oil may also be conveniently used as a solvent where the product is to be employed asv a lubricating oil additive, since in this way a mineral oil concentrate of the product will result which is readily soluble in oil and at the same time the step of removing the solvent upon completion 'of the reaction is avoided. Where. a solvent other than mineral oil is used, the reaction mixture is filtered andtopped at elevated temperature and reduced pressure to remove the solvent.

The proportion of wax-alkylated hydroxy aromatic compound and phosphorus pentoxide used in the reaction can be varied between from about 1 to about 3 mols of the wax-alkylated hydroxy aromatic compound to 1 mol of phosphorus pentoxide, although the preferred products are obtained by the use of 3 mols of the waxalkylated hydroxy aromatic compound per molof phosphorus pentoxide.

The use of wax phenol as the wax-alkylated hydroxy aromatic compound reactant in the preparation of the additives herein contemplated is preferred. However, other wax alkylated hydroxy aromatic compounds may be satisfactorily used, such as alpha-naphthol, betanaphthol, resorcinol, catechol, hydroquinone, alpha-anthrone, beta-anthrone and the cresols.

The exact nature of the products of the invention are not known, however, it'may be stated, without intent to limit the invention, tha.t they. are believed to be mixtures of wax aryl-substituted phosphoric. acids, such as monoand di-wax aryl phosphoric acid and wax aryl pyrophosphoric acid. In order to more fully illustrate themanner of preparation of these products. the following specific examples are presented.

PREPARATION OF'WAX-PHENOL (3-14) war; has absorbed about 14%, by weight, of chlorine.

A sufficient quantity of this chlorinated wax to provide 3 atomic proportions of chlorine is then heated to a temperature varying from just above its melting point to not over 150 F. One mol of phenol (CsHsOH) is then mixed with the chlorowax. The mixture is then heated to about 150 F. and a quantity of anhydrous aluminum chloride, corresponding to-about 3% of the weight'of the chlorowax in the mixture, is slowly added withactive stirring. The rate of addition of the aluminum chloride should be sufficiently slow to avoid violent foaming and during the addition the temperature should beheld at about 150 F. After the aluminum chloride has been added the temperature of the mixture may be increased slowly over a period of 'froml'S to 25 minutes to a temperature of about 250 F. andthen should be more slowly increased to'about. 350 F. To control the evolution of HCl gas, the temperature of the mixture is: preferably raised from 250 F. to 350 F. at'a rate of approximately one degree. per minute, the whole heating operation occupying'approximately two hoursfrom thetime of adding the: aluminum chloride. If the emission of HCl gas has not ceased when'the final temperature is reached, the mixture may be held at 350 F. for a short'time to allow completionof the reaction. However, to avoid possible cracking of the wax, the mixture should not be heated appreciably above 350 F., nor should it be held at that temperature for any extendedilength of time;

It is important that all unreacted, or non-alkylated, phenol remaining in the reaction mixture, as well as aluminum chloride, be. removed. This.v can be. conveniently effected by washing the. product severaltimes with a mixture of water and an alcohol, such as butanol, preferably at elevated temperature, say 175 F. The product may then be treated with steam. This latter step will insure complete removal of the unreacted material and also dry the product.

It will be understood that a wax-substituted phenol prepared according to the above procedure in which a quantity of chlorowax containing three atomic proportions of chlorine and having a chlorine content of 14% is reacted with one mol of phenol, is designated as waxphenol (314). Similarly, wax-phenol (310) and wax-phenol (1-10) may also be prepared by the reaction of sufiicient amounts of chlorinated wax, containing 10 per cent by weight of chlorine, to provide 3 atomic proportions and 1 atomic proportion of chlorine per mol of phenol, respectively, in the reaction and are useful in the invention. In general, the amount of chlorowax, containing from about 10 to 18 per cent by weight of chlorine, used in the reaction is sufiicient to supply between 1 and 4 atomic proportions of chlorine per mol of phenol used.

In preparing the Wax-phenol (l-10) used in the following Examples V and VI, the procedure just described for the preparation of wax-phenol (3-14) was modified slightly in that an excess of phenol (100%) was used for reaction with the chlorowax (an amount to provide one atomic proportion of chlorine) in order to insure as complete a conversion as possible to monowax alkylated phenol.

Further details relative to the procedure for the preparation of wax phenols suitable for use herein may be had by reference to Patent No. 2,191,499, issued February 27, 1940, to Orland M. Reiif.

EXAMPLE I Wax phenol (310)-P2O5 product (3:1)

Reaction mixture (mol ratio of wax phenol:

The wax phenol (3-10) and toluene were placed in a 2-liter, 4-necked, round bottom flask equipped with a reflux condenser, thermometer and mechanically driven stirrer. After heating to 100 C., P205 was gradually added to the mixture over a 4-hour period. Following this. the temperature of the mixture was held at 100 C. for a period of 8 hours to insure complete reaction. The product was then filtered through Hi-Flo, a diatomaceous earth filter aid. and the filtrate was topped to 150 C. under diminished pressure to remove the toluene solvent. The residue, representing the finished product, contained 1.77% phosphorus and had a neutralization number of 47.2.

EXAMPLE II Wax phenol (314)-P2O product (3:1)

Reaction mixture (mol ratio of wax phenol:

Wax phenol (3-14) (phenol content=approx.

11.9%) grams 300 P205 0 18 Toluene ml 300 Procedure Same as described in Example I. The product contained 2.2% phosphorus and had a neutralization number of 62.5.

EXAMPLE III Procedure The wax phenol (3-14) and mineral oil were placed in a l-liter, 4-necked, round bottom flask equipped with a reflux condenser, thermometer and mechanically-driven stirrer. After heating to C., P205 was gradually added to the mixture over a 2 /2 hour period. Following this, the temperature of the mixture was maintained at 100 C. for an 8-hour period to insure complete reaction. The reaction mixture was then filtered through a layer of Hi-Flo, a diatomaceous clay filter aid, contained in a heated Buchner funnel. The filtrate, representing the finished product, contained 1.53% phos phorus and had a neutralization number of 44.2.

EXAMPLE IV Wax phenol (3-14)-P205 product (1:1)

Grams Reaction mixture (mol ratio of wax phenol:

P2O5=1:l)

Wax phenol (3-14) (phenol content=approx. 200

11 9'7 P205 36.0 S. A. E. 20 mineral oil 400 Procedure Same as described in Example III. The product contained 2.02% phosphorus and had a neutralization number of 40.3.

EXAMPLE V Wax phenol (110)-P205 product (3:1)

Reaction mixture (mol ratio of wax phenol:

Wax phenol (1-10) (phenol content=approx.

) grams 400 P205 do 35.5

Toluene ml 400 Procedure Same as described in Example I. The product contained 2.96% phosphorus and had a neutralization number of 77.3.

EXAMPLE VI Wax phenol (1-10)-P205 product (2:1

Grams Reaction mixture (mol ratio of wax phenol:

Wax phenol (1-10) (phenol content=approx.

17.4%) P205 24.4 Toluene 185 Procedure Same general procedure as described in Example I. The product contained 4.59% phosphorus and had a neutralization number of 96.3.

Same general procedure as described in Example I. The product contained 1.48% phosphorus and had a neutralization number of 52.4.

EXAMPLE VIII 192 stock* phenol (310)-P205 product (2:1)

Grams Reaction mixture (mol ratio of 192 /2 stock phenol:

192 /2 stock phenol (3-10) (phenol content=approx. 7.6%) 500 P20 28.5 Toluene 500 S. A. E. 10 mineral oil 500 "A wax fraction derived from petroleum.

"thermometer, "and a mechanically-driven stirrer. '-"-heating"to"-'95-"1'00" C., POswasgraiduallyadded-over a I l-hour' period. Following *-this, "the Ptenmerature of the 192 /2 stock-*phenol"' ('2-'-"10) '(phenolcontent=ap- "prox. l=1i9% 1 @S. .A. ;E. 20.mineral:-.oil 20 *-.A was: fracttonederived mm petroleum.

Pracedure same'generalprocedure as described in Example 'TII. 'mhe aproduct contained 056572: 'zphophorus and had a neuz-itralization'anumber .282.

Ihezfollowing-exangples sshow lthe preparation of'gprodi325 nets of phosphorus pentoxide with alkylated phenols in which the alkyl substitutents are of non-wax origin. These products were used in the tests hereinafter described as a bas'is for'romparing "their effectiveness as-petroleum addihives with iithat 10f .the wax tphen'olsphosphorus tpentoxide :30

;products xQf the previous examples. X -Diamylp7zen0l-Bz'0 pr0duct('3 21 A iGrams .React-ion (mixture (mol. ratio 10f .diamylpheuol 1P2O5=3 1 I 'Di-tert-an ylphenol .234 "P505 27 Procedure .The-diamylphenol was placedin .a lsliter, -4-necked,

round bottom 'fia'sk equipped with .a reflux condensirft, a ter mixture was held at 95 C. for 2 hours and at 150 C. for 3 /2 hours. The product was then diluted with 150 ml. of benzene, filtered through Hi-Flo and toppedto 180 C. under diminished pressure-toremovethe-solvent.

The residue, representing the finished gproduct, contained 50 8.3% phosphorus and had a neutralizationmumber.ofllfi. EXAMPLE' XI DodecylphenoL-PzOa 'produc't (3:!)

Procedure Same general procedure as described in Example I. The product contained 6.48% phosphorus and had a neutralization number 015M190.

.TTrioetaiieejlphenbl- EiQs proiiuct .(3 :11 ziReaeti'on imixtnre :(mol iratio :of ti'ioctadecylphenol:

,zlirioctadecylphenol i'(:phenol content=-:approx.

IQ-24%;) .;grams 5 PiQ min .321 Toluene -:-ml .75

L'Rm'cedure Same xgenenal pmcedure :as described :in Example I. The prnduct contained Til-583% :phosphoms and zhad a :neutralizat-ion .number of :5-4a6.

' ocrade'cylph emi'bl zfls*product (3i-I,-)

. v {Grams :Reaction mixture mol .ratio tdf woctadecylphenol:

1?.z05--l3.:'I.)--

I0ctadecylphenol 40 1 .205 "15.0

Procedure :The octadecylphenol .was g'placedin 250 i4-neeked, round bottom .rflask =.containing .a .reflux :teondenser, ithfll" mometer and mechanically-driven stirrer. After heat- :ing Eto 210.0" =.C., rP2Q5 was gradually .added @over .a tminute period. .T he imixture was then .heated for 6% Zhour-s at :100 C. .il 'he reaction mixture was-thenfiltered .thnough .Hi-Flo.nontained in rarheated :Buchner sfunnel. The ifiltrate, .;re presenting "the .-fin-ished ;produ ct, rcontained .5 1.% .phosphorus and had aEneutr-alization number of :14 l

EVAEUATION *OF PRODUCTS i120 demonstrate -;the .efiectiveness of .the uvax lphenol- .phosphorusj pentuxicle sreact-ion products aasextreme pressure regents ands-as pourgpoint: depressants in imineral lu- '40 ebricatingoils, and pariticularly to .show their .superionity sin :these respects .over the alkyl phenolgphosphorus pent- "oxide .--products .in :which .theeallsyl groups .are .o'fnon-wax \origin, .oil blends of .each of the products prepared in -the vforegoing"examples .wene ,prepared:andsubjectedto tests.

:P. KITEST To determine their extreme pressure character, the oil blends .weressubjected .to..the Almen Bin test, described by Mougey and Almen, "Proc. "PLI. 1931, page 77. This test, which is designed to determine the ultimate "*load ca'rrying capacity of a lubricant, is widely used in the evaluation :c'Sf'EP. lubricants. ln' fliis test the iAlmen 'test machine ismsed. The test lubricant is placed in a small metal "cup with a one fourth --inch -drill -rod shaft rotatingin .a.split1'bushing.at 600 .R. P. M. Weights are added at Ill-secondintervals 1o -a loading lever working "to applygpressure onlthesplittbusliirrg. .Theiklmen value is expressed as the number of :weightsnteqdiredto cause -=sizure-df-the bushing. *Eac'h' weightweighs' l poundsand is equivalent to 1,000 ,pounds per:square flinch qpressure. Table lashows the results obtainediinztliis .tesbwith the various *oil 'blends. The oil was =a'solvent-"refined, M' i'd- Continent, SAE 30 grade oil having a pour "point of 20 F. and.akinematic'viscosity"at'2'l0 F. of 1136125.

.-Tab'le.zl

1 ALSITEMLPOur' Point, 'g. M R ti QgncnxWii Almen .1 o e o, p .emen Ex.-No.-- ProduetZBlendedlnGil X @Phenalmio Hflmmmted mg? Basis) 1 3% Wt. 0.25% Wt.

Concn. Concn.

Nor 2 +20 +20 Wax Phenol (340)-1105 321 3- 0 12 Wax Phenol (3l4)-P20s-. 3:1 3. 0 21 Wax Phenol (3-14)-Pa0 2:1 3. 0 11 30 -20 Wax Phenol (3 14)-Pa05.. 1 3. 0 10 -25 Wax Phenol (110)-P:0s-- 3:1 3. 0 23 25 +20 Wax Phenol (110)-Pa05 211 3. 0 11 -20 +20 192% Stk. Phenol (340) PaOs- 3:1 3.0 16 25 20 192% Stk. Phenol (3-10) PaOL 211 3.0 13 -30 -20 192% Stk. Phenol (210)-P205- 3:1 3.0 13 25 -15 Diamvlohenol-Pzos 3 :1 3. 0 5 +20 +25 Dodeeylnhenol-Pzos 3 =1 3. 0 6 +25 +20 Trioetadeeylphenol-Pzor 3:1 3. 0 15 0 +20 1 Reaction product undiluted with oil used as a solvent medium in the preparation thereof.

The test data in Table I illustrate the improvement in E. P. capacity of the oil, effected by the use of the waxalkylated phenol-phosphorus pentoxide products over the products obtained with the alkylated phenols in which the alkyl substituent is of non-wax origin.

The data further show that the products derived from the wax phenol substituents are very. efiective as pour point depressants, whereas the products having the lower alkyl substituents are not.

To demonstrate the outstanding quality of the products of this invention as rust-inhibitors in gasoline, the products of several of the examples given hereinabove were subjected to the modified ASTM D 66547-T test. The conditions of this test are recognized as being much more severe than actual pipeline conditions in that a much higher amount of water is present and it is generally accepted that test specimens exposed to the severe rusting conditions of this test for 48 hours are rusted to substantially the same degree as those exposed to a products pipeline for 30 to 60 days. The ASTM test used herein was modified to the extent of lowering the test temperature from 140 F. to 80 F. Briefly, this test involves stirring a mixture of 300 ml. of the gasoline under test with 30 ml. of dissolved water at a temperature of 140 F. with a cylindrical steel specimen immersed therein. After 48 hours contact with the gasoline-water mixture, the specimen is examined to determine whether or not it has rusted.

As is well known in the art, an important limitation upon the use of a rust-preventative in gasoline is its effect on gum formation. As a generalization, it can be said that rust-preventatives are non-volatile in nature and increase the amount of gum formed by the amount of preventative added. Consequently, a rust preventative useful in gasoline is one which is effective in concentration no greater than about 0.008 weight per cent non-volatile residue. When a sample of finished gasoline containing normal amounts of dye, tetraethyl lead, antioxidants, etc. and the indicated amounts of the products of the examples were subjected to the aforesaid ASTM test, the results obtained were as shown in Table II. It will be seen from the table that the wax-alkylated phenol-P205 products are much more effective as rust-preventatives in gasoline than the alkylated phenol-P205 products wherein the alkyl portions are of non-wax origin.

necessarily relatively small, the smallest effective amounts being the preferred amounts. In general, amounts within the range of from about 0.0003% up to, about 0.008% are suitable. On the other hand, when .utilized in lubricating oils as pour point depressants or extreme pressure additives larger amounts ranging from about 1% to about 5% are desirable, although amounts ranging from 0.25% up to about 10% may be used.

Concentrated oil solutions of the additives, containing from about 25 to about 75 per cent of the additives are also contemplated. Such concentrates are desirable for marketing, in that they save shipping space and provide a readily soluble form of the additive products for blending with oil in preparing the finished oil compositions.

The products of the invention may, of course, be used in petroleum oil fractions containing other additives designed to improve the character thereof in different respects, such as anti-oxidants, detergents, V. I. improvers, etc.

This invention is not intended to be limited in any way by the specific examples or illustrative procedures delscribed herein, but only as indicated in the following claims.

I claim:

1. As a new composition of matter, the product obtained from the reactioninvolving 1 mol of phosphorus pentoxide with approximately 3 mols of wax phenol at a temperature of from about C. to about 150 C.

2. A mineral lubricating oil containing a minor proportion, snfiicient to improve the extreme pressure character and depress the pour point of said oil, of the prodnot obtained from the reaction involving 1 mol.of phosphorus pentoxide and approximately 3 mols of wax phenol at a temperature of from about 50 C. to about 150 C.

3. A gasoline containing a minor proportion, from about 0.0003% to about 0.008%, by weight, of the product obtained from the reaction involving 1 mol of phosphorus pentoxide and approximately 3 mols of wax phenol at a temperature of from about 50 C. to about 150 C.

Table II MODIFIED ASTM D 66547-T TEST ON FINISHED MOBILGAS Concentration Wt.,Percent Active Ingredient Ex. No. Product Added None .0010 .0005 .0004 .00033 .0003 .00027 .0002

None FaiL.

II Wax Phenol (314)-PO5 (3:1) Pass Pass Pass Fail.

Reaction Product I Wax Phenol (310)-Pz05 (3:1) Pass Pass Pass.

Reaction Product. X Diamyl Phenol-P 0 (3:1) He Fail.

action Product. XI Dodecyl Phenol-P20 (3:1) Re- Fail action Product. XIII Octadecyl Phenol-P205 (3:1) d0 Fail Reaction Product.

The amount of the additive products of this inventiog 3;; References Cited in the file of this patent to be added to the petroleum oil fraction will depen upon the particular fraction, i. e. whether a lubricating UNITED STATES PATENTS oil or a gasoline and, if a lubricating oil, on the particu- 2,272,668 Honel Feb. 10, 1942 131' improvement desired. Thus, as p o1nted out previously, 2,365,938 Cook et a1 Dec. 26, 1944 when used in gasolines as rust mhlbitors, the amounts are 2,506,310 Mikeska May 2, 1950 

2. A MINERAL LUBRICATING OIL CONTAINING A MINOR PRO PORTION, SUFFICIENT TO IMPROVE THE EXTREME PRESSURE CHARACTER AND DEPRESS THE POUR POINT OF SAID OIL. OF THE PRODUCT OBTAINED FROM THE REACTION INVOLVING 1 MOL OF PHOSPHORUS PENTOXIDE AND APPROXIMATELY 3 MOLS OF WAX PHENOL AT A TEMPERATURE OF FROM ABOUT 50* C. TO ABOUT 150* C. 